Symmetrical polyfluoroisoalkoxyalkyl quaternary ammonium sulfates

ABSTRACT

1. A COMPOUND OF THE FORMULA   (F3C-CF(-CF3)-O-(CF2)S-(CH2)T-Q)(+) (-)O-SO2-O-(CH2)T-   (CF2)S-O-CF(-CF3)2   WHEREIN Q IS A QUANTERNARY AMMONIUM RADICAL AND S AND T ARE INTEGERS FROM 1 TO 10.

3,839,343 SYMMETRICAL POLYFLUOROISOALKOXYALKYL QUATERNARY AMMONIUM SULFATES Louis G. Anello, Orchard Park, and Richard F. Sweeney, Elma, N.Y., assignors to Allied Chemical Corporation, New York, NY. No Drawing. Filed Nov. 10, 1969, Ser. No. 875,547 Int. Cl. C0711 31/48 US. Cl. 260294.8 R 6 Claims ABSTRACT OF THE DISCLOSURE Symmetrical quaternary ammonium sulfates having the formula wherein Q is a quaternary ammonium radical and R; has the formula wherein ,R R are fluorine, chlorine or perhaloalkyl; X X, are hydrogen, fluorine, chlorine or bromine; r is an integer from 1-2, m and n are integers from -20, and p is an integer from 0-1. These compounds are surface active agents and can be used to form oil repellent coatings on textiles.

SUMMARY OF THE INVENTION The compounds of this invention are symmetrical quaternary ammonium sulfates of the formula wherein Q is a quaternary ammonium radical and R is a polyfluoroisoalkoxyalkyl radical of the formula wherein (a) R R R and R can be independently selected from the group consisting of fluorine, chlorine and perhaloalkyl groups of 1 to 10 carbon atoms, or when taken together R -R may form a perhalocycloalkyl structure, the halo portions of RrRq being fluorine or chlorine, with the provisos that each carbon atom of R R contain at least one fluorine atom, R and R cannot both be chlorine and R and R cannot both be chlorine; preferably R -R are fluorine or perfluoroalkyl groups of 1 to 3 carbon atoms, most preferably R -R, are fluorine.

(b) X X X and X independently can be hydrogen, fluorine, chlorine or bromine, provided that each X X group do not include more than two chlorine atoms or one bromine atom, and when X and X independently are each hydrogen or fluorine, each of X and X independently may be CF R wherein R is a halogen, alkyl or haloalkyl radical of 1 to 8 carbon atoms in which the halogen atoms are fluorine, chlorine or bromine, the (X X CCX X and (X X CCX X,) moieties may be the same or different; preferably X X., independently can be hydrogen, fluorine or chlorine.

(c) r is an integer from 1-2, m and n are integers from 0-20, the sum of m and n is 0-20, preferably m and n United States Patent O are 0-10, p is an integer from 0-1, with the proviso that when p is 0, n must be at least one and X and X in the (X X CCX X moiety must be hydrogen.

The criticality in the structure of the above described compounds is in the polyfiuoroisoalkoxyalkyl tail portion of the molecule wherein an ether oxygen atom links a fluorinated carbon atom attached to two fluoroalkyl groups and at least one CF group.

The novel compounds of this invention are surface active agents. They show good detergency, wetting properties, foaming capability, and foam stability at low concentrations. In addition they are useful as surface tension depressants for aqueous solutions and organic solvents, leveling agents in wax formulations, fire extinguishing agents for hydrocarbon-type fires, and oil repellent coatings for textiles.

DETAILED DESCRIPTION OF THE INVENTION The compounds of this invention can be prepared by reacting a fluorinated dialkyl sulfate of the formula (R,O) SO wherein R, is as defined above, with a tertiary amine. Preferably the dialkyl sulfate is added to the amine. Generally the mole ratio of tertiary amine to dialkyl sulfate varies from about 1:1 to about 10:1.

The reaction preferably is carried out at about atmospheric pressure, although higher pressures can also be used. The reaction temperature can range from about 25 C. to about 200 C., preferably from about 50 C. to about C. Reaction time will vary depending on the particular starting materials and on the temperature and pressure. Generally reaction time is from about 0.5 hours to about 5 hours.

Preferably Q is a quaternary ammonium radical of the formula wherein w is an integer from 0-1; when w is one R R and R independently can be alkyl (straight chain or branched) of 1 to 12 carbon atoms, preferably of 1 to 6 carbon atoms; hydroxyalkyl of 1 to 12 carbon atoms, preferably of 1 to 6 carbon atoms, cycloalkyl of up to 6 carbon atoms, aryl of up to 9 carbon atoms, or R and R can be joined to form a saturated heterocyclic structure of up to 6 carbon atoms; and when w is 0, R and R can be joined to form an aromatic heterocyclic structure of up to 9 carbon atoms. Preferably not more than one of R R and R is cycloalkyl or aryl. Most preferably Q is pyridine or a trialkyl amine of up to 12 carbon atoms in which each alkyl group independently contains from 1 to 6 carbon atoms.

Suitable tertiary amines are well known and include, for example, trialkyl amines such as trimethylamine, triethylamine, tributyl amine, tridodecylamine, methyldiethylamine dimethylhexylamine and the like; hydroxyalkyl amines such as hydroxyethyldimethylamine, trihydroxyethylamine, and the like; cycloalkyl amines such as dimethylcyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine and the like; aromatic amines such as benzyldimethylarnine, dimethylaniline, di n propylaniline triphenylamine and the like; heterocyclic amines, such as pyridine, 4-hydroxyethylpyridine, quinoline, picoline, lutidine, N-methylmorpholine, N-methylpiperidine and the like.

The fluorinated dialkyl sulfates and their method of preparation are described in copending US. application Ser. No. 659,867, filed Aug. 11, 1967, now US. Pat. No. 3,562,310, the pertinent subject matter of which is hereby incorporated by reference.

Essentially the fluorinated dialkyl sulfates are prepared by reacting the corresponding fluorinated iodides with oleum or with sulfur trioxide in about a 1:1 mole ratio. Temperatures ranging from about C. to about 200 C. and pressures from about 1 to 300 atmospheres can be employed. It is preferred to operate at such temperature and pressure that at least a portion of the iodide reactant is maintained in the liquid phase.

The fluorinated iodides may be prepared by reacting an appropriate ketone with an ionizable fluorine salt, e.g. C'sF or KF, to form a fluorinated organic salt which is then reacted with a halogen other than fluorine (e.g., iodine, bromine) and an appropriate olefin to form telogen iodides, as illustrated below.

The telogen iodides can then 'be reacted with additional appropriate olefins. These reactions can be initiated by heat, e.g., temperatures from about 100 C. to 350 C., or by a free radical initiator such as azobisisobutyronitrile, benzoyl peroxide and the like. These reactions are described in greater detail in copending U.S. application of Anello et al., Ser. No. 633,359, filed Apr. 25, 1967, the pertinent subject matter of which is hereby incorporated by reference.

The telogen iodides having only one CF group linking the oxygen and iodine atoms can be prepared by reacting a telogen iodide having two CF groups with sulfur trioxide to form an acid halide. This reaction is carried out at temperatures between about 50175 C. Preferably, an excess of S0 is used and sufficient pressure is employed to maintain the reactants in the liquid phase. The acid halide is hydrolyzed to the acid by refluxing in water. The resulting acid has a single carbon atom linking the oxygen atom with the carboxy group. This acid can then be converted to the corresponding telogen iodide possessing a single carbon atom linking the oxygen and iodide atoms by the well known Hunsdiecker reaction which involves reacting the acid with alkali-free silver oxide (Ag O) to form the silver salt, followed by reaction of the silver salt with powdered iodine to form the iodide This telogen iodide can then be telomerized with one or more olefins. Illustrative procedures are shown as follows:

1110 (CF3)1CFOCF:COF (CFa)zCFOCFaCOOH I: (C FahCFO CFiCOOAg (CFahCFOOFzI GFFCm (OFQ OFOGFAOFZCFQJ (C FQZCF O C F2(CFzCFz)m(CH1CF2) nI E (CF3)2CFOCF2(CFzCF2)m(CF2CHz)nI It should be noted that the above-noted telomerization reaction produces two products (A) and (B). The (A) product is obtained in about a 95% yield. The (B) product is obtained in about a 5% yield. The (A) and (B) products can be separated by conventional procedures. For example, dehydroiodinating the (A) and (B) product mixture with KOH at -150 C. preferentially converts product (A) to the corresponding olefin which can then be readily separated from product (B) by distillation.

For special case where m and n in formula I are 0 and p and r are one, the iodide starting materials can be obtained by reacting a telogen of the formula with S0 esterifying the resulting reaction products, re-

ducing the ester to the alcohol with LiAlH as reducing agent and reacting the alcohol with p-toluene sulfonyl chloride and metallic iodide to form the iodide containing one CF group and one CH group.

Preferred telomerizable unsaturated materials are selected from the group consisting of CF =CF CF =CH CF =CClF, CF CF=CF and CH =CH which yield (X X CCX X moieties of the formula and CH --CH respectively. Other suitable telomerizable unsaturated materials include the following:

CHCl=CFCF Many more suitable telomerizable unsaturated compounds, subject to the restrictions of the definition for the compounds of formula (I) given above, will readily occur to one of the ordinary skill in the art.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred class of compounds within the scope of the invention occurs when R; in formula (I) has the formula wherein R -R are as defined above and s and tare integers from 1-20, preferably from 1-10, most preferably 1 is an integer from 1-3. The preferred class of compounds can be prepared by the above described methods of preparation.

Specific examples of embodiments of the novel compounds of the invention i.e.,

(Rtovo 020 R1,

are those wherein R; and Q have the following formulas:

TABLEContinued R: Q 11 C(o Fm CFO(C 1)2( z)x-' C (0 Fa):

(0 F3)1CFO(CF2)10(CH2)3 (EH: ,N

CH3 12 FQC-C1 E r-o-oormo F,o rygom-o mom- FzCCl 13 0 F920 F 0 0 F2)@(C F -O F2) 0H,01-1Br our H H 1r,o,\ /c'o N\ /C1'Ig o-o 14 (CFgC1)gCFO(C Fz)2(CH2)z- H2 H2 The invention can be more fully understood by refer- EXAMPLE 3 ence to the following examples. Analyses are in percent by weight.

EXAMPLE 1 Preparation of To 15 g. (0.15 mole) of triethylamine was slowly added g. (0.034 mole) of After a slight exotherm, the stirred mixture was heated and maintained at 8082 C. for 2 hours. Excess amine, 12 g., was decanted from the fluorinated tetraalkylammonium alkyl salt produced. The salt was Washed with three portions of anhydrous diethyl ether and then heated to 50 C. under a reduced pressure of 25 mm. for 4 hours to remove unreacted amine and dialkyl sulfate ester. There was recovered 21 g. (0.025 mole) of a tan pasty solid having a melting point of 96 98 C.

Analysis for C F H NSO gave the following results: Calculated: C, 29.16; F, 50.77; H, 2.77; S, 3.88. Found: C, 29.28; F, 49.32; H, 2.39; S, 4.25.

EXAMPLE 2 Preparation of To 26 g. (0.26 mole) of triethylamine was slowly added g. (0.038 mole) of (CF CFO CF CF CH CH O] 80 After a slight exotherm the temperature was raised to 80-85 C. and maintained there for 2 /2 hours. The fluorinated tetraalkylammonium alkyl salt, 27 g. (0.0027 mole), was recovered as a tan pasty solid having a melting point of l02104 C.

Analysis for 'C F H NSO gave the following results: Calculated: C, 28.15; F, 55.71; H, 2.25; S, 3.12. Found: C, 28.53; F, 53.85; H, 2.36; S, 3.75.

Preparation of i (C F1020 F O CFZCFzCH CHzN o mocmcmomcmoro on To 15 g. (0.19 mole) of pyridine was slowly added 25 g. (0.34 mole) of [(CF CFOCF CFgCH CH O] After a slight exotherm to 38 C., the stirred mixture was heated and maintained at 80-85 C. for 2 hours. Excess amine (13 g.) was recovered by heating the mixture to 80 C. under a reduced pressure of 1 mm. for 4 hours. There was recovered 26 g. (0.032 mole) of a light tan crystalline solid having a melting point of 6770 C.

Analysis for C F H NSO gave the following results: Calculated: C, 27.21; F, 52.17; H, 1.62; S, 4.00. Found: C, 26.85; F, 52.49; H, 1.73; S, 4.22.

EXAMPLE 4 Preparation of EXAMPLE 5 Preparation of [wrmoro ortormcnzonmj was added 15 g. (0.19 mole) of pyridine. The mixture was then heated to -105 C. for 2 hours. On cooling, excess amine was decanted from the pasty-solid lower layer. The product was heated to 80 C. under a reduced pressure of 1 mm. to remove additional unreacted amine, There was recovered 14 g. (0.012 mole) of a tan crystalline solid having a melting point of 99101 C.

Analysis for C2'1F38H13SNO6 gave the following results: Calculated: C, 27.00; F, 60.11; H, 1.08; N, 1.16; S, 2.66. Found: C, 26.84; F, 59.93; H, 1.25; N, 1.32; S, 2.84.

EXAMPLE 6 Table I below lists illustrative sulfate salts that have been prepared and shows the reduction in surface tension produced when a small amount is dissolved in water; the first row giving the surface tension value in the absence of additive. All values were measured at 25 C.

TABLE I Surface tensions (dynes/cm.) of water with and without additives Value without additive 72. 3 Amount of additive (percent by wt.) 1. 0.5 0.1 0.05 Additive compounds of example:

EXAMPLE 7 The sulfate salts were tested as textile treating agents. Samples of cotton print cloth were padded with 0.5% aqueous solutions of the fiuorochemieals, squeezed to remove excess solution (100% wet pick-up), then dried at about 160 C. for 4 minutes. The oil repellency was measured and the results are shown in Table 11 below.

The procedure employed in measuring the oil repellency is described, for example, on pages 323-4 of the April 1962 edition of the textile Research Journal. This procedure involves gently placing on the treated fabric drops of mixtures of mineral oil and n-heptane in varying proportions. The drops are allowed to stand on the treated fabric undisturbed for 3 minutes, after which the wetting and penetration of the fabric is visually observed. The number corresponding to the mixture containing the highest percentage of heptane which does not penetrate or wet the fabric is considered to be the oil repellency rating of the treated fabric. A rating of 70 or higher is considered good.

10 TABLE 11 Compound of: Oil repellency Example 1 Example 2 Example 3 100 Example 4 Example 5 130 We claim: 1. A compound of the formula C133 CFS [F O(CFz)S(CHz)tO] o s o2o oH.).)or2)s0-oF F3 F3 wherein Q is a quaternary ammonium radical and s and t are integers from 1 to 10.

2. The compound of claim 1 wherein t is an integer from 1 to 3.

3. The compound of claim 2 wherein Q is pyridine.

4. The compound of claim 3 wherein s is 2 and t is 2.

5. The compound of claim 3 wherein s is 4 and t is 2. 6. The compound of claim 3 wherein s is 6 and t is 2.

References Cited UNITED STATES PATENTS 3,335,163 8/1967 Tesoro et al. 260-456 3,647,887 3/1972 Anello et a1 260 611 A 3,651,073 3/1972 Kahn et al. 260297 R 3,651,120 3/1972. Anello et al. 260458 3,674,798 7/1972 Price et al 260-2948 R 3,706,773 12/1972 Anello et al. 260458 3,739,033 6/1973 Anello et al. 260-615 F 3,766,274 10/ 1973 Anello et al 260-584 C OTHER REFERENCES Karrer: Organic Chemistry, 2nd English Edition, Elsevior Publishing Co. (New York), pp. 901-902 1946) ALAN L. RO'IMAN, Primary Examiner US. Cl. X.R.

8l16.2; 1l7l38.5; 252-2, 8.75; 260247.l, 283 S, 286 Q, 293.9, 458

UNITED STATES PATENT OEFICE CERTIFICATE OF CORRECTION Patent No. 3,839 ,3 l3 Dated October 1, 1974 ln'ventofls) LOUIS o. 'ANELLO" and RICHARD F. SWEENEY It is certified that error appears in the above-identified pat ent and that said Letters Patent are hereby corrected as shown below:

Col. 3, vline 59 after, "iodide" insert Col 4, last formula that part which reads "Bl I Q I I E-c-R v a F-C-Rg should read F-C-O- l v F-C-O- I I v- F-C-R R Ru --5 Cols. 5-6 under heading "R First formula that part which reads "FC-OCF2C2-'-" should read FCOCF2CH2- Secohd formula that paft which reads "F FC-C1 FC-O HFORM PO-IOSO (was) USCOMM-DC 60376-P69 *-U.S. GDVERNMENT PRINTING OFFICE: 1959 O-36G-334 O UNIT D STATES PATENT OFFICE O age 2 CERTIFICATE OF CORRECTION .Patent No. 3,839 ,3 43, 7 a -e October 1 197 4 Inventor(s) LOUIS G. 'A ELLO and RICHARD F. SWEENEY It is ertified that error appears in the above-identified patent and that 'said Letters Patent are hereby corrected as shown below:

should read E FC J-Cl' FC-o FC-F Fifth formula that part which reads "(CF CF Fc-F- FC-O- Y PCT-F should read (CF2)2CF3 i FC-F FC-O- FC-F Seventh formula that part which reads "501 FORM po'mso (10459) C I v USCOMM-DC wave-p69 v 1 u.s. GOVERNMENTPRIINTING OFFICE 1 I969 o-sss-ssa i Page 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,839 3M3 Y ated October 1, 197M Inventofls) LOUIS G. ANELLO and RICHARD F. SWEENEY It is certified that error appears in the ab0ve--identified patent: and .that said Letters Patent are hereby corrected as shown below:

should read 9P3 Y, I 911 2 ELF-O v v v 3 Col. 8, line 727 .':'[:(,CH3)2CFO" should read [(CF3)E2CFO Col. 10, claim 1 1' oF v oF I E 3-O-(CF )S(CH )tO OEO O(CH )CF )SO(3F CF3 CF3" should read Signed and sealed this 11th day of February. 1975.

(SEAL) v A at c I c v tte g C. MARSHALL DANN RUTH C. MASON I Commissioner of Patents Attesting Officer and Trademarks j FORM PC4050 (10'69) a v E USCOMM-DC 60376-P69 U.S. GOVERNMENT PRINTING OFFICE: I969 O-355-334 Patent No. 3,839,3 8 Dated October 1, 197U' Inventods) LOUIS G. ANELLO and RICHARD F. SWEENEY It is certified that er ror appear s in the above-identified pat ent and that said Letters Patent are hereby corrected as shown below:

001. 3, line 59 after iodide insert Col 4, last formula that part which reads Cols. 5-6 under heading "R First formula that part which reads "FC-OCF2C2-'-" I should read FC-OCF2CH2- Second formula that part which reads "If h I FC--Cl Fo-o FORM PO-1050 (10-69) USCOMM-DC seam-pe I fl U.S. GOVERNMENT PRINTING OFFICE: 1969 0-366-334 UNITED STATES PATENT OFFICE Page 2 CERTIFICATE OF CORRECTION Patent No. 3, 39 3% 7 Dated October 1, 197M Inventor(s) LOUIS G. ANELLO and RICHARD F. SWEENEY It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

should read 1? F( 3Cl Fo-o FC-F Fifth formula that part which'reads JF )2CF I 7 Q Fey-F- I Fc-o- I FC-F should read (?F CF Fo-F FCE-OQ Seventh formula that part which reads "C F FORM PC4050 (1069) V uscoMM-Dc scan-Pe i F us eovznumam 'vnm'rms omcz I959 o-aes-su Patent NO. 3,839 ,3'u3 Dated October 1, 197A Inventofls) LOUIS G. ANELLO and RICHARD F SWEENEY t is certified that error appears in the above -identified patent and that said Letters Patent are hereby corrected as shown below:

should read (3P3 w F-o-o V s o v Col. 8, line 72 i'[(CH c o" should read [(CF3) 2CFO Col. 10, claim 1 9F?) v E 3E 3-O(CF )S(CH )'cO OEO O(CH )CF )SO-(3F should read a F CF Signed and sealed this 11th day of February, 1975.

(SEAL) Attest: g

C. MARSHALL DANN RUTH C MASON l Commissioner of Patents Attesting Officer 4 7 and Trademarks FORM PC4050 (wse) Y US'COMM-DC 60376-F'6Q Q .5. GOVERNMENT PRINTING OFFICE, 1959 0-356-334 

1. A COMPOUND OF THE FORMULA 